CN110184570A - A kind of preparation method of solid-oxide fuel cell connector protective film - Google Patents
A kind of preparation method of solid-oxide fuel cell connector protective film Download PDFInfo
- Publication number
- CN110184570A CN110184570A CN201910483499.9A CN201910483499A CN110184570A CN 110184570 A CN110184570 A CN 110184570A CN 201910483499 A CN201910483499 A CN 201910483499A CN 110184570 A CN110184570 A CN 110184570A
- Authority
- CN
- China
- Prior art keywords
- connector
- protective film
- solid
- preparation
- fuel cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/021—Cleaning or etching treatments
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/085—Oxides of iron group metals
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
- C23C14/325—Electric arc evaporation
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/54—Controlling or regulating the coating process
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/58—After-treatment
- C23C14/5846—Reactive treatment
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0223—Composites
- H01M8/0228—Composites in the form of layered or coated products
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The present invention relates to solid oxide fuel cell technical field more particularly to a kind of preparation methods of solid-oxide fuel cell connector protective film.The preparation method, which comprises the steps of:, is placed in solid-oxide fuel cell connector in cavity, and arc source is selected to carry out aura cleaning to the connector；Inert gas is filled with to the cavity and adjusts the vacuum degree of the cavity, arc ion plating is carried out to the connector, forms Mn/Co protective film on the surface of connector；(Mn, Co) is generated to the Mn/Co protective film oxidation on connector surface3O4Spinel oxide protective film selects arc source to carry out aura cleaning to the connector or, the preparation method comprises the steps of: that solid-oxide fuel cell connector is placed in cavity；It is filled with the gaseous mixture of oxygen or oxygen and inert gas to the cavity, chamber vacuum degree is adjusted by the oxygen or gaseous mixture that are filled with, arc ion plating is carried out to the connector, forms (Mn, Co) on the surface of connector3O4Spinel oxide protective film.
Description
Technical field
The present invention relates to solid oxide fuel cell technical fields more particularly to a kind of solid oxide fuel cell to connect
The preparation method of junctor protective film.
Background technique
In recent years, the decline of traditional fossil energy reserves such as petroleum, coal causes international oil price to remain high, in addition global
Climate warming, problem of environmental pollution are more serious, tap a new source of energy and reasonable energy utilization, raising energy utilization rate have become
The emphasis of various countries' research.Fuel cell is not required to that directly electric energy can be converted by chemical energy by fuel combustion process, effectively mentions
High fuel availability, is a kind of more efficient, environmentally friendly energy utilization patterns, wherein solid oxide fuel cell (Solid
Oxide fuel cell, SOFC) because of its fuel availability height, fuel wide adaptation range, pollution-free, cost is relatively low, noiseless etc.
Feature becomes the emphasis studied at present.Bridge of the connector as anode and cathode transmitting electronics between adjacent cell, accounts for about entire battery
The 33% of heap cost, connector will not only have good matching with other constituent elements of battery, more to adapt to the work of complicated atmosphere
Make environment with maintaining a long-term stability property, the stability of connector and chemical property to solid-oxide fuel cell stack play to
Important role is closed, wherein metal connector can not only play in anode-supported SOFC system supports other battery components, passes
The effect of conductive gas also has higher heating conduction, can will promptly react generated heat and conduct, Yi Mianju
The excessively high service life to reduce fuel cell of portion's temperature, however in the environment of solid oxide fuel cell work, gold
Belong to connection surface layer generation oxide Cr easy to oxidize2O3, make surface resistance (the ASR:Area Surface of connector
Resistivity) increase, reduce the electric conductivity of connector, and the volatilization of Cr element makes the poisoning of cathode to influence making for battery
With the service life, solve the problems, such as that this most simple effective method is exactly to prepare connector protective film.MnxCo3-xO4Serial spinelle is protected
Cuticula is free of rare earth element, while possessing the thermal matching fabulous with ferritic stainless steel, significantly reduces connector in yin
Surface resistance in the oxidizing atmosphere of pole, the external diffusion for effectively preventing Cr element reduces poisoning of cathode phenomenon, to improve electricity
The service life in pond.Chinese patent (Zhang Huihui, Zhu Ming, Wang Zhihua, a kind of preparation side of the anti-corrosion cobalt-manganese spinel coating of conduction
Method, China Patent No.: CN105332029B) disclose a kind of conductive anti-corrosion cobalt manganese point crystalline substance of solid-oxide fuel cell connector
The preparation method of stone coating, this method preparation coating be well combined with substrate, simple process, with good electric conductivity with it is resistance to
Corrosion, it was demonstrated that the feasibility of cobalt-manganese spinel coating, but the coating stress prepared by way of electrochemical deposition is complicated
It is be easy to cause cracking, and electric current and voltage potentially unstable coating layer thickness occur unevenly thus the phenomenon that influencing performance.China
Patent (Ma Xinxin, Tang Guangze, Zhen Shuying, a kind of solid oxide fuel cell stainless steel connector spinel oxide protection
The preparation method of coating, China Patent No.: CN105239050B) disclose a kind of solid oxide fuel cell stainless steel connection
The preparation method of body spinel oxide protective coating, the protective coating compactness is good, good with basal body binding force and thickness can
It adjusts, but magnetron sputtering adds subsequent anneal processing to prepare the mode complex process of spinel oxide, unsuitable industry with high costs
Metaplasia produces.
Summary of the invention
(1) technical problems to be solved
The present invention provides a kind of preparation method of solid-oxide fuel cell connector protective film, preparation method benefits
Manganese cobalt class protective film is prepared with the mode of arc ion plating, the protection of manganese cobalt spinel-like oxide is ultimately formed after being oxidized
Film, this method using arc ion plating solve cobalt manganese spinel-like coating layer thickness in the prior art unevenly so as to cause
The defects of connector performance is poor, and effectively improve solid-oxide fuel cell connector high-temperature oxidation resistant, antikathode poisoning
Etc. performances.
(2) technical solution
In order to achieve the above object, the main technical schemes that the present invention uses include:
The preparation method specifically includes the following steps:
S1: solid-oxide fuel cell connector is placed in a cavity, and arc source is selected to fire soild oxide
Expect that battery connecting structure carries out aura cleaning；
S2: it is filled with inert gas to the cavity, the vacuum degree of the cavity is adjusted by the inert gas, to the connector
Arc ion plating is carried out, forms Mn/Co protective film on the surface of connector；
S3: aoxidizing the Mn/Co protective film on connector surface, generates fine and close (Mn, Co)3O4Spinel oxide
Protective film；
Alternatively, the preparation method comprises the steps of:
Step 1: solid-oxide fuel cell connector is placed in a cavity, and arc source is selected to fire soild oxide
Expect that battery connecting structure carries out aura cleaning；
Step 2: being filled with the gaseous mixture of oxygen or oxygen and inert gas to the cavity, pass through the oxygen or gaseous mixture being filled with
The vacuum degree for adjusting the cavity carries out arc ion plating to the connector, forms (Mn, Co) on the surface of connector3O4
Spinel oxide protective film.
According to the present invention, the material of the solid-oxide fuel cell connector be 430 stainless steels, 304 stainless steels,
The siderochrome base Alfer such as Crofer22APU alloy is one such.
According to the present invention, further include before step S1 or step 1 to the solid-oxide fuel cell connector into
The step of row surface treatment, the surface treatment include that oil removing, removal of impurities, mechanical polishing and ultrasonic cleaning are one such or several
Kind.
In accordance with the present invention it is preferred that this four steps of surface treatment carry out in order, if without above step to even
Junctor surface is cleaned, and arc ion plating process intermediate ion will occur with connector binding force not enough leads to showing for demoulding
As.
According to the present invention, in step S1 or step 1, in the arc source, the molar ratio of Mn and Co be 0~80:100~
20。
According to the present invention, in step S1 or step 1, the chamber vacuum degree is 9 × 10-5Pa~1 × 10-3Pa, in cavity
Enough vacuum degrees ensure that electronics and ion have enough energy ionized molecules.
According to the present invention, in step S1 or step 1, the connection temperature is 100 DEG C~500 DEG C, and cavity temperature is more than
At 100 DEG C, the water in cavity is effectively evaporated, and then achieve the effect that decontamination.
According to the present invention, in step S1 or step 1, the aura cleaning bias is 200V~600V, and cleaning bias is selected
Big voltage ensure that impurity is cleaned completely.
According to the present invention, in step S2 or step 2, the chamber vacuum degree is 9 × 10-5Pa~1 × 10-1Pa.The cavity
Vacuum degree is the chamber vacuum degree after being filled with atmosphere, not the background vacuum of cavity, the brightness in background vacuum and step S2
Light cleaning chamber vacuum degree is consistent.
According to the present invention, in step S2 or step 2, the connection temperature is 100 DEG C~500 DEG C, and connection temperature exists
The thermal stress that film layer is mainly influenced in coating process can generate certain heat in the bombardment of coating process intermediate ion on connector,
It will increase film layer thermal stress if connection temperature and its temperature difference are excessive, to cause film layer cracking phenomena.
According to the present invention, in step S2 or step 2, the arc current is 20A~200A, arc source striking current used
Bigger, deposition velocity is faster, but also results in that film layer is not fine and close enough, and internal stress is excessive simultaneously.
According to the present invention, in step S2 or step 2, the substrate bias is -300V~0V.
According to the present invention, in step S2 or step 2, the plated film time is not less than 10min, and coating speed is by arc current
It determines, the time determines the thickness of film layer.
According to the present invention, the method for oxidation described in step S3 are as follows:
Method A, the connector that surface is formed with to Mn/Co protective film assemble in pile, in solid oxide fuel electricity
In the test in pond or operational process, make Mn/Co protective film by in-situ oxidation at (Mn, Co)3O4Spinel oxide protective film；
Or:
Method B, the connector that surface is formed with to Mn/Co protective film have been placed on heated oxide in oxygen atmosphere, protect Mn/Co
Cuticula is oxidized to (Mn, Co)3O4Spinel oxide protective film.
According to the present invention, in method A, the oxidizing temperature of in-situ oxidation is 400 DEG C to 800 in test or operational process
℃。
According to the present invention, in method B, the heated oxide temperature is 200 DEG C to 1000 DEG C.
According to the present invention, described to be heated to the time aoxidized after oxidizing temperature not less than 30min in method B.
(3) beneficial effect
The beneficial effects of the present invention are: the present invention is prepared for solid oxide fuel cell connection using arc ion plating
The Mn/Co protective film of body, this method simple process and low cost are easy to produce in batches, while can be in solid oxide fuel electricity
After pond connector assembles in pile, in-situ oxidation prepares (Mn, Co) in test process3O4Spinel oxide protective film, structure
Stablize and good with connector binding force, solid-oxide fuel cell connector high-temperature oxidation resistant, anti-yin can be effectively improved
The performances such as pole poisoning.
Detailed description of the invention
Fig. 1 is the Mn/Co protective film XRD constituent analysis that in embodiment 1 prepared by arc ion plating；
Fig. 2 is the Mn/Co protective film SEM figure that in embodiment 1 prepared by arc ion plating；
Fig. 3 is in-situ oxidation preparation (Mn, Co) in embodiment 13O4Spinel oxide protective film XRD constituent analysis；
Fig. 4 is in-situ oxidation preparation (Mn, Co) in embodiment 13O4Spinel oxide protective film SEM figure.
Specific embodiment
In order to preferably explain the present invention, in order to understand, below by specific embodiment, present invention work is retouched in detail
It states.
Embodiment 1
Prepare a piece of industrial 430 ferritic stainless steel SOFC connectors with a thickness of 1mm, mass fraction
Wt%:Cr 16.5, Mn 0.6, Si 0.5, C 0.1, Fe bal., wt%: weight percent, bal: remaining.By connector according to
After secondary progress oil removing, removal of impurities, mechanical polishing, ultrasonic cleaning, clean solid-oxide fuel cell connector is obtained.
Mn and Co molar ratio is selected to vacuumize after installing arc block, connector to cavity, mesh for the arc source of 50:50
Marking chamber vacuum degree is 1 × 10-4Pa, while cavity is heated, target temperature is 200 DEG C, in impurity such as evaporation vapor
The binding force that connection temperature reinforces ion and connector is improved while gas.Reach target value in chamber vacuum degree and temperature
Afterwards, arc switch is opened, the aura that bias is 800V is carried out and cleans, aura scavenging period is 30min, if still there is fire at electric arc
Flower, which splashes out, can suitably increase aura scavenging period.
After aura cleaning, argon gas is passed through cavity, adjustment argon gas amount makes chamber vacuum degree be maintained at 0.1Pa, cavity temperature
Be maintained at 200 DEG C it is constant, setting arc current be 30A, substrate bias be -100V, carry out arc ion plating.Plating run is set
Arc block is closed after being set to every continuous coating 120min, releases chamber vacuum situation, reduces cavity temperature to room temperature, closing machine electricity
The 430 stainless steel connectors prepared are taken out in source.
The 430 stainless steel connector assembling solid oxide fuel cells heaps that will directly have manganese cobalt spinel-like protective film
In, cathode is passed through air, and anode is passed through 3%H297%Ar mixed gas, pile running temperature is set as 650 DEG C, SOFC pile
Into working condition, Mn/Co protective film in-situ oxidation in pile test process generates (Mn, Co)3O4Spinel oxide protection
Film.
Oxidation film layer thickness at any time has been carried out to solid fuel cell heap respectively and ASR variation test, test result are aobvious
Show: with oxidization time, parabolically rule is grown the oxidation film film layer total thickness variations rule prepared with this method, in preceding 300h
It mushrooms out to 14 μm, and slightly grows into 14.8 μm in 1000h hour later；Film layer surface resistance is by initial simultaneously
10mΩ/cm2, 14m Ω/cm is risen to by 300h2, then arrive 18m Ω/cm of 500h2, finally arrive 21m Ω/cm of 1000h2,
Its oxidation behavior is fitted with formula, the results showed that resistance is up to 89.15404m Ω/cm behind 40000h2, it is less than and connects
Junctor 100m Ω cm2Requirement.
Embodiment 2
Prepare a piece of industrial 430 ferritic stainless steel SOFC connectors with a thickness of 1mm, mass fraction
Wt%:Cr 16.5, Mn 0.6, Si 0.5, C 0.1, Fe bal., wt%: weight percent, bal: remaining.By connector according to
After secondary progress oil removing, removal of impurities, mechanical polishing, ultrasonic cleaning, clean solid-oxide fuel cell connector is obtained.
Mn and Co molar ratio is selected to vacuumize after installing arc block, connector to cavity, mesh for the arc source of 30:70
Marking chamber vacuum degree is 1 × 10-4Pa, while cavity is heated, target temperature is 200 DEG C, in impurity such as evaporation vapor
The binding force that connection temperature reinforces ion and connector is improved while gas.Reach target value in chamber vacuum degree and temperature
Afterwards, arc switch is opened, the aura that bias is 500V is carried out and cleans, aura scavenging period is 30min, if still there is fire at electric arc
Flower, which splashes out, can suitably increase aura scavenging period.
After aura cleaning, argon gas is passed through cavity, adjustment argon gas amount makes chamber vacuum degree be maintained at 0.1Pa, cavity temperature
Be maintained at 200 DEG C it is constant, setting arc current be 30A, substrate bias be -10V, carry out arc ion plating.Plating run is set
Arc block is closed after being set to every continuous coating 120min, releases chamber vacuum situation, reduces cavity temperature to room temperature, closing machine electricity
The 430 stainless steel connectors prepared are taken out in source.
Directly the 430 stainless steel connectors prepared are fitted into solid-oxide fuel cell stack.Cathode is passed through air,
Anode is passed through 3%H297%Ar mixed gas, pile running temperature is set as 650 DEG C, and SOFC pile enters working condition.Mn/
Co protective film in-situ oxidation in pile test process generates (Mn, Co)3O4Spinel oxide protective film.
Oxidation film layer thickness at any time has been carried out to solid fuel cell heap respectively and ASR variation test, test result are aobvious
Show: with oxidization time, parabolically rule is grown the oxidation film film layer total thickness variations rule prepared with this method, in preceding 300h
It mushrooms out to 17 μm, and slightly grows into 18.3 μm in 1000h hour later；Film layer surface resistance is by initial simultaneously
15mΩ/cm2, 20m Ω/cm is risen to by 300h2, then arrive 23m Ω/cm of 500h2, finally arrive 25m Ω/cm of 1000h2,
Its oxidation behavior is fitted with formula, the results showed that resistance is up to 94.84624m Ω/cm behind 40000h2, it is less than and connects
Junctor 100m Ω cm2Requirement.
Embodiment 3
Prepare a piece of industrial 430 ferritic stainless steel SOFC connectors with a thickness of 1mm, mass fraction
Wt%:Cr 16.5, Mn 0.6, Si 0.5, C 0.1, Fe bal., wt%: weight percent, bal: remaining.By connector according to
After secondary progress oil removing, removal of impurities, mechanical polishing, ultrasonic cleaning, clean solid-oxide fuel cell connector is obtained.
Mn and Co molar ratio is selected to vacuumize after installing arc block, connector to cavity, mesh for the arc source of 50:50
Marking chamber vacuum degree is 1 × 10-4Pa, while cavity is heated, target temperature is 200 DEG C, in impurity such as evaporation vapor
The binding force that connection temperature reinforces ion and connector is improved while gas.Reach target value in chamber vacuum degree and temperature
Afterwards, arc switch is opened, the aura that bias is 500V is carried out and cleans, aura scavenging period is 30min, if still there is fire at electric arc
Flower, which splashes out, can suitably increase aura scavenging period.
After aura cleaning, argon gas is passed through cavity, adjustment argon gas amount makes chamber vacuum degree be maintained at 0.1Pa, cavity temperature
Be maintained at 200 DEG C it is constant, setting arc current be 30A, substrate bias be -10V, carry out arc ion plating.Plating run is set
Arc block is closed after being set to every continuous coating 30min, releases chamber vacuum situation, reduces cavity temperature to room temperature, closing machine electricity
The 430 stainless steel connectors prepared are taken out in source.
Directly the 430 stainless steel connectors prepared are fitted into solid-oxide fuel cell stack.Cathode is passed through air,
Anode is passed through 3%H297%Ar mixed gas, pile running temperature is set as 650 DEG C, and SOFC pile enters working condition.Mn/
Co protective film in-situ oxidation in pile test process generates (Mn, Co)3O4Spinel oxide protective film.
Oxidation film layer thickness at any time has been carried out to solid fuel cell heap respectively and ASR variation test, test result are aobvious
Show: with oxidization time, parabolically rule is grown the oxidation film film layer total thickness variations rule prepared with this method, in preceding 300h
It mushrooms out to 10 μm, and slightly grows into 12.8 μm in 1000h hour later；Film layer surface resistance is by initial simultaneously
17mΩ/cm2, 22.5m Ω/cm is risen to by 300h2, then arrive 27m Ω/cm of 500h2, finally arrive the 33m Ω of 1000h/
cm2, its oxidation behavior is fitted with formula, the results showed that resistance is up to 96.50603m Ω/cm behind 40000h2, small
In connector 100m Ω cm2Requirement.
Embodiment 4
Prepare a piece of industrial 430 ferritic stainless steel SOFC connectors with a thickness of 1mm, mass fraction
Wt%:Cr 16.5, Mn 0.6, Si 0.5, C 0.1, Fe bal., wt%: weight percent, bal: remaining.By connector according to
After secondary progress oil removing, removal of impurities, mechanical polishing, ultrasonic cleaning, clean solid-oxide fuel cell connector is obtained.
Selecting Mn/Co molar ratio is the arc source of 50:50, is vacuumized after installing arc block, connector to cavity, target
Chamber vacuum degree is 1 × 10-4Pa, while cavity is heated, target temperature is 200 DEG C, in impurity gas such as evaporation vapor
The binding force that connection temperature reinforces ion and connector is improved while body.Reach target value in chamber vacuum degree and temperature
Afterwards, arc switch is opened, the aura that bias is 500V is carried out and cleans, aura scavenging period is 30min, if still there is fire at electric arc
Flower, which splashes out, can suitably increase aura scavenging period.
After aura cleaning, argon gas is passed through cavity, adjustment argon gas amount makes chamber vacuum degree be maintained at 0.1Pa, cavity temperature
Be maintained at 200 DEG C it is constant, setting arc current be 30A, substrate bias be -10V, carry out arc ion plating.Plating run is set
Arc block is closed after being set to every continuous coating 120min, releases chamber vacuum situation, reduces cavity temperature to room temperature, closing machine electricity
The 430 stainless steel connectors prepared are taken out in source.
Directly the 430 stainless steel connectors prepared are fitted into solid-oxide fuel cell stack.Cathode is passed through air,
Anode is passed through 3%H297%Ar mixed gas, pile running temperature is set as 750 DEG C, and SOFC pile enters working condition.Even
Junctor protective film in-situ oxidation in pile test process, which generates, has manganese cobalt spinel-like oxide film.
Oxidation film layer thickness at any time has been carried out to solid fuel cell heap respectively and ASR variation test, test result are aobvious
Show: with oxidization time, parabolically rule is grown the oxidation film film layer total thickness variations rule prepared with this method, in preceding 300h
It mushrooms out to 16 μm, and slightly grows into 17 μm in 1000h hour later；Film layer surface resistance is by initial 10m simultaneously
Ω/cm2, 15m Ω/cm is risen to by 300h2, then arrive 19.7m Ω/cm of 500h2, finally arrive 22.8m Ω/cm of 1000h2,
Its oxidation behavior is fitted with formula, the results showed that resistance is up to 92.84627m Ω/cm behind 40000h2, it is less than and connects
Junctor 100m Ω cm2Requirement.
Embodiment 5
Prepare a piece of industrial 430 ferritic stainless steel SOFC connectors with a thickness of 1mm, mass fraction
Wt%:Cr 16.5, Mn 0.6, Si 0.5, C 0.1, Fe bal., wt%: weight percent, bal: remaining.By connector according to
After secondary progress oil removing, removal of impurities, mechanical polishing, ultrasonic cleaning, clean solid-oxide fuel cell connector is obtained.
Mn and Co molar ratio is selected to vacuumize after installing arc block, connector to cavity, mesh for the arc source of 50:50
Marking chamber vacuum degree is 1 × 10-4Pa, while cavity is heated, target temperature is 200 DEG C, in impurity such as evaporation vapor
The binding force that connection temperature reinforces ion and connector is improved while gas.Reach target value in chamber vacuum degree and temperature
Afterwards, arc switch is opened, the aura that bias is 800V is carried out and cleans, aura scavenging period is 30min, if still there is fire at electric arc
Flower, which splashes out, can suitably increase aura scavenging period.
After aura cleaning, argon gas is passed through cavity, adjustment argon gas amount makes chamber vacuum degree be maintained at 0.1Pa, cavity temperature
Be maintained at 200 DEG C it is constant, setting arc current be 30A, substrate bias be -100V, carry out arc ion plating.Plating run is set
Arc block is closed after being set to every continuous coating 120min, releases chamber vacuum situation, reduces cavity temperature to room temperature, closing machine electricity
The 430 stainless steel connectors prepared are taken out in source.
The 430 stainless steel connectors with Mn/Co protective film are placed in 650 DEG C of heat preservation 10h, heating rate in air atmosphere
For 4 DEG C/min, cooling rate is 2 DEG C/min, is had (Mn, Co)3O4The fuel cell of spinel oxide protective film connects
Body.
Solid fuel cell heap has carried out oxidation film layer thickness at any time respectively and ASR variation test, test result are shown:
With oxidization time, parabolically rule is grown the oxidation film film layer total thickness variations rule prepared with this method, rapid in preceding 300h
18 μm are grown into, and slightly grows into 19.4 μm in 1000h hour later；Simultaneously film layer surface resistance by initial 15m Ω/
cm2, 20m Ω/cm is risen to by 300h2, then arrive 23.7m Ω/cm of 500h2, finally arrive 24.8m Ω/cm of 1000h2, use
Formula is fitted its oxidation behavior, the results showed that resistance is up to 94.79483m Ω/cm behind 40000h2, it is less than connection
Body 100m Ω cm2Requirement.
Embodiment 6
Prepare a piece of industrial 430 ferritic stainless steel SOFC connectors with a thickness of 1mm, mass fraction
Wt%:Cr 16.5, Mn 0.6, Si 0.5, C 0.1, Fe bal., wt%: weight percent, bal: remaining.By connector according to
After secondary progress oil removing, removal of impurities, mechanical polishing, ultrasonic cleaning, clean solid-oxide fuel cell connector is obtained.
Mn and Co molar ratio is selected to vacuumize after installing arc block, connector to cavity, mesh for the arc source of 50:50
Marking chamber vacuum degree is 1 × 10-4Pa, while cavity is heated, target temperature is 200 DEG C, in impurity such as evaporation vapor
The binding force that connection temperature reinforces ion and connector is improved while gas.Reach target value in chamber vacuum degree and temperature
Afterwards, arc switch is opened, the aura that bias is 800V is carried out and cleans, aura scavenging period is 30min, if still there is fire at electric arc
Flower, which splashes out, can suitably increase aura scavenging period.
After aura cleaning, argon gas and oxygen are passed through cavity, adjust the amount of argon gas and oxygen (argon gas is 1:1 with oxygen ratio)
So that chamber vacuum degree is maintained at 0.1Pa, cavity temperature be maintained at 200 DEG C it is constant, setting arc current is 30A, substrate bias is-
100V, carries out arc ion plating, and plating run closes arc block after being set as every continuous coating 120min, releases chamber vacuum shape
Condition reduces cavity temperature to room temperature, and closing machine power supply takes out the 430 stainless steel connectors prepared, and directly obtaining has
(Mn,Co)3O4The fuel battery connectors of spinel oxide protective film.
Oxidation film layer thickness at any time has been carried out to solid fuel cell heap respectively and ASR variation test, test result are aobvious
Show: with oxidization time, parabolically rule is grown the oxidation film film layer total thickness variations rule prepared with this method, in preceding 300h
It mushrooms out to 21 μm, and slightly grows into 22.1 μm in 1000h hour later；Film layer surface resistance is by initial simultaneously
17mΩ/cm2, 22m Ω/cm is risen to by 300h2, then arrive 24.5m Ω/cm of 500h2, finally arrive the 25.3m Ω of 1000h/
cm2, its oxidation behavior is fitted with formula, the results showed that resistance is up to 97.17682m Ω/cm behind 40000h2, small
In connector 100m Ω cm2Requirement.
The present invention is prepared for solid-oxide fuel cell connector Mn/Co protective film, the party using arc ion plating
Method simple process and low cost is easy to produce in batches, while can assemble in pile in solid-oxide fuel cell connector
Afterwards, in-situ oxidation prepares (Mn, Co) in test process3O4Spinel oxide protective film, stable structure and with connector binding force
Well, the performances such as solid-oxide fuel cell connector high-temperature oxidation resistant, antikathode poisoning can be effectively improved.
It is to be appreciated that describing the skill simply to illustrate that of the invention to what specific embodiments of the present invention carried out above
Art route and feature, its object is to allow those skilled in the art to can understand the content of the present invention and implement it accordingly, but
The present invention is not limited to above-mentioned particular implementations.All various changes made within the scope of the claims are repaired
Decorations, should be covered by the scope of protection of the present invention.
Claims (9)
1. a kind of preparation method of solid-oxide fuel cell connector protective film, it is characterised in that: the preparation method packet
Containing following steps:
S1: solid-oxide fuel cell connector is placed in a cavity, selects arc source to solid oxide fuel electricity
Pond connector carries out aura cleaning；
S2: being filled with inert gas to the cavity, the vacuum degree of the cavity adjusted by the inert gas, carries out to the connector
Arc ion plating forms Mn/Co protective film on the surface of connector；
S3: oxidation processes are carried out to the Mn/Co protective film on connector surface, generate fine and close (Mn, Co)3O4Spinel oxide
Protective film；
Alternatively, the preparation method comprises the steps of:
Step 1: solid-oxide fuel cell connector is placed in a cavity, selects arc source to solid oxide fuel electricity
Pond connector carries out aura cleaning；
Step 2: being filled with the gaseous mixture of oxygen or oxygen and inert gas to the cavity, adjusted by the oxygen or gaseous mixture that are filled with
The vacuum degree of the cavity carries out arc ion plating to the connector, forms (Mn, Co) on the surface of connector3O4It is sharp brilliant
Graphite/oxide protective film.
2. preparation method according to claim 1, it is characterised in that: the material of the solid-oxide fuel cell connector
Matter is that the siderochrome base Alfers such as 430 stainless steels, 304 stainless steels, Crofer22APU alloy are one such.
3. preparation method according to claim 1, it is characterised in that: before step S1 or step 1 further include to described
The step of solid-oxide fuel cell connector is surface-treated, the surface treatment include oil removing, removal of impurities, mechanical polishing
It is one such or several with being cleaned by ultrasonic.
4. preparation method according to claim 1, it is characterised in that: in step S1 or step 1, to the solid oxidation
When object fuel battery connectors carry out aura cleaning, the molar ratio of Mn and Co in the arc source are 0~80:100~20, chamber
Body vacuum degree is 9 × 10-5Pa to 1 × 10-3Pa, connection temperature are 100 DEG C to 500 DEG C, and it is 200V- that aura, which cleans bias,
600V。
5. preparation method according to claim 1, it is characterised in that: in step S2 or step 2, to the connector into
When row arc ion plating, chamber vacuum degree is 9 × 10-5Pa to 1 × 10-1Pa, connection temperature are 100 DEG C to 500 DEG C, electricity
Arc current is 20A to 200A, and substrate bias is -300V to 0V, and the arc ion plating time is not less than 10min.
6. preparation method according to claim 1-5, it is characterised in that: the method for oxidation described in step S3
Are as follows:
Method A, the connector that surface is formed with to Mn/Co protective film assemble in pile, in solid oxide fuel cell
In test or operational process, make Mn/Co protective film by in-situ oxidation at (Mn, Co)3O4Spinel oxide protective film；
Or:
Method B, the connector that surface is formed with to Mn/Co protective film have been placed on heated oxide in oxygen atmosphere, make Mn/Co protective film
It is oxidized to (Mn, Co)3O4Spinel oxide protective film.
7. preparation method according to claim 6, it is characterised in that: in method a, in situ in test or operational process
The oxidizing temperature of oxidation is 400 DEG C to 800 DEG C.
8. preparation method according to claim 6, it is characterised in that: in method B, the oxidizing temperature of heated oxide is
200 DEG C to 1000 DEG C.
9. preparation method according to claim 6, it is characterised in that: in method B, carry out oxygen after being heated to oxidizing temperature
The time of change is not less than 30min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910483499.9A CN110184570B (en) | 2019-06-04 | 2019-06-04 | Preparation method of solid oxide fuel cell connector protective film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910483499.9A CN110184570B (en) | 2019-06-04 | 2019-06-04 | Preparation method of solid oxide fuel cell connector protective film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110184570A true CN110184570A (en) | 2019-08-30 |
| CN110184570B CN110184570B (en) | 2021-11-23 |
Family
ID=67720236
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910483499.9A Active CN110184570B (en) | 2019-06-04 | 2019-06-04 | Preparation method of solid oxide fuel cell connector protective film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110184570B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112018417A (en) * | 2020-07-16 | 2020-12-01 | 哈尔滨工业大学（深圳） | Method for preparing electrolyte layer or electrolyte barrier layer of solid oxide fuel cell |
| CN112195444A (en) * | 2020-08-17 | 2021-01-08 | 徐州华清智能装备有限公司 | Preparation method of solid oxide fuel cell stack connector protective coating |
| CN113067007A (en) * | 2021-03-19 | 2021-07-02 | 哈尔滨工业大学（深圳） | Solid fuel cell composite sealing layer and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653858A (en) * | 2012-05-28 | 2012-09-05 | 哈尔滨工业大学深圳研究生院 | Method for preparing MnCo spinel protecting film by magnetron sputtering and subsequent oxidation |
| CN104393315A (en) * | 2014-10-09 | 2015-03-04 | 大连海事大学 | Solid oxide fuel cell stainless steel bipolar connector and manufacturing method thereof |
| CN104878354A (en) * | 2015-01-14 | 2015-09-02 | 东北大学 | Coating for flat-plate intermediate-temperature solid oxide fuel cell metal connector |
-
2019
- 2019-06-04 CN CN201910483499.9A patent/CN110184570B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102653858A (en) * | 2012-05-28 | 2012-09-05 | 哈尔滨工业大学深圳研究生院 | Method for preparing MnCo spinel protecting film by magnetron sputtering and subsequent oxidation |
| CN104393315A (en) * | 2014-10-09 | 2015-03-04 | 大连海事大学 | Solid oxide fuel cell stainless steel bipolar connector and manufacturing method thereof |
| CN104878354A (en) * | 2015-01-14 | 2015-09-02 | 东北大学 | Coating for flat-plate intermediate-temperature solid oxide fuel cell metal connector |
Non-Patent Citations (3)
| Title |
|---|
| PAUL GANNON ET AL.: "Advanced PVD protective coatings for SOFC interconnects", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| S. MOLIN ET AL.: "Microstructural and electrical characterization of Mn-Co spinelprotective coatings for solid oxide cell interconnects", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
| 曹希文等: "固体氧化物燃料电池金属连接体保护涂层的制备方法概述", 《中国陶瓷》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112018417A (en) * | 2020-07-16 | 2020-12-01 | 哈尔滨工业大学（深圳） | Method for preparing electrolyte layer or electrolyte barrier layer of solid oxide fuel cell |
| CN112195444A (en) * | 2020-08-17 | 2021-01-08 | 徐州华清智能装备有限公司 | Preparation method of solid oxide fuel cell stack connector protective coating |
| CN113067007A (en) * | 2021-03-19 | 2021-07-02 | 哈尔滨工业大学（深圳） | Solid fuel cell composite sealing layer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110184570B (en) | 2021-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106374116B (en) | High-entropy alloy composite coating and technique on a kind of fuel battery metal double polar plate | |
| CN110184570A (en) | A kind of preparation method of solid-oxide fuel cell connector protective film | |
| Wu et al. | Recent development of SOFC metallic interconnect | |
| CN110684946B (en) | Metal bipolar plate high-conductivity corrosion-resistant protective coating and preparation method and application thereof | |
| CN110137525A (en) | A kind of fuel battery metal double polar plate coating and technology of preparing | |
| CN102473935A (en) | Titanium material for solid polymer fuel cell separator, and process for production thereof | |
| CN102653858B (en) | Method for preparing MnCo spinel protecting film by magnetron sputtering and subsequent oxidation | |
| CN101257119A (en) | Double polar plates for fuel battery and method for making surface azote nickel-chromium thin film | |
| JP2009263794A (en) | Stainless steel separator for fuel cell and method of manufacturing the same | |
| Yokokawa | Report of five-year NEDO project on durability/reliability of SOFC stacks | |
| CN104878354A (en) | Coating for flat-plate intermediate-temperature solid oxide fuel cell metal connector | |
| CN100513619C (en) | Ferritic stainless steel containing rare earth element yttrium for solid-oxide fuel battery | |
| CN104269569B (en) | The surface modification of metals connector and its manufacture method of a kind of SOFC | |
| CN101519740A (en) | Ni-Mo-Cr alloy for metal connecting body of cathode Cr poison resisting intermediate-temperate solid oxide fuel battery | |
| CN108914060A (en) | A kind of preparation method of fuel battery double plates surface protection coating | |
| US20100122911A1 (en) | Method for coating metallic interconnect of solid oxide fuel cell | |
| CN110034273B (en) | Sn-based sulfide and/or nitride modified tin oxide thin-film lithium battery cathode and preparation and application thereof | |
| CN111477899A (en) | Conductive corrosion-resistant metal bipolar plate for fuel cell and preparation method thereof | |
| CN106784916A (en) | A kind of fuel cell long-life bipolar plates with surface titanium molybdenum nickel C film and preparation method thereof | |
| CN111342073A (en) | Conductive corrosion-resistant titanium metal bipolar plate for fuel cell and preparation method thereof | |
| CN110047658A (en) | Carbon, electrode material of sulphur codope and preparation method thereof | |
| CN110875482A (en) | Method for preparing carbon film on surface of stainless steel bipolar plate by using graphite as carbon source | |
| CN113445014A (en) | Surface functional coating process for hydrogen fuel cell titanium bipolar plate | |
| CN103956592A (en) | Grounding grid NiP-DLC composite corrosion resisting protection coating and preparing method | |
| KR102187088B1 (en) | Photosynthetic microbial fuel cell containing ZnO nanorod pattern and manufacturing method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |